JP2711973B2 - Manufacturing method of zinc-based electroplated steel sheet with excellent corrosion resistance - Google Patents

Manufacturing method of zinc-based electroplated steel sheet with excellent corrosion resistance

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Publication number
JP2711973B2
JP2711973B2 JP5004095A JP409593A JP2711973B2 JP 2711973 B2 JP2711973 B2 JP 2711973B2 JP 5004095 A JP5004095 A JP 5004095A JP 409593 A JP409593 A JP 409593A JP 2711973 B2 JP2711973 B2 JP 2711973B2
Authority
JP
Japan
Prior art keywords
corrosion resistance
plating
steel sheet
zinc
vanillin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP5004095A
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Japanese (ja)
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JPH06212481A (en
Inventor
文男 山崎
芳雄 新藤
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Nippon Steel Corp
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Nippon Steel Corp
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Priority to JP5004095A priority Critical patent/JP2711973B2/en
Publication of JPH06212481A publication Critical patent/JPH06212481A/en
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Expired - Fee Related legal-status Critical Current

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Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【産業上の利用分野】本発明は自動車,家電などに用い
られるCrを含有する耐食性に優れた亜鉛系電気めっき
鋼板の製造方法に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a zinc-containing electroplated steel sheet containing Cr and having excellent corrosion resistance, which is used for automobiles and home appliances.

【0002】[0002]

【従来の技術】電気亜鉛めっき鋼板は、自動車,家電,
建材用途を中心に広く使用されている。このうち、自動
車用途では、寒冷地帯における冬期の道路凍結防止用の
散布岩塩による車体腐食を防止するために、より高度な
耐食性が要求されている。亜鉛めっき鋼板の耐食性向上
は、亜鉛のめっき量(付着量)の増加で可能であるが、
これは溶接性や加工性の点で問題が多い。そこで亜鉛そ
のものの溶解を抑制し亜鉛めっきの寿命を延ばす方法と
して、多くの合金めっきが提案されている。中でもF
e,Ni,Coを合金成分として含有するZn系合金め
っきは、その良好な裸耐食性や塗装後耐食性が認めら
れ、実用化されている。また、特開昭61−27039
8号公報,特開昭62−54099号公報,特開平3−
120393号公報などに開示されているように、Zn
ないしZn系合金めっき中にCrを含有させる試みもな
されているが、耐食性においてZn−Ni合金めっきや
Zn−Fe合金めっきを凌駕するには到っていない。
2. Description of the Related Art Electrogalvanized steel sheets are used in automobiles, home appliances,
Widely used mainly for building materials. Of these, in automobile applications, higher corrosion resistance is required in order to prevent vehicle body corrosion due to scattered rock salt for preventing road freezing in winter in cold regions. Corrosion resistance of galvanized steel sheet can be improved by increasing the amount of zinc plating (adhesion).
This has many problems in terms of weldability and workability. Therefore, many alloy platings have been proposed as a method of suppressing the dissolution of zinc itself and extending the life of zinc plating. Above all, F
Zn-based alloy plating containing e, Ni, and Co as alloy components is recognized for its good bare corrosion resistance and corrosion resistance after painting, and has been put to practical use. Further, Japanese Patent Application Laid-Open No. 61-27039
No. 8, Japanese Patent Application Laid-Open No. 62-54099, Japanese Patent Application Laid-Open
As disclosed in JP-A-120393 and the like, Zn
Attempts have also been made to include Cr in the Zn-based alloy plating, but this has not been superior to Zn-Ni alloy plating or Zn-Fe alloy plating in corrosion resistance.

【0003】[0003]

【発明が解決しようとする課題】亜鉛と共にCrを析出
させる試みはCr3+やCr6+イオンを用いて従来から行
なわれているが、単純浴からは微量のCrが析出するの
みであり、Cr濃度や電流密度の増加によって数%のC
rを析出させても、良好な外観が得られないだけでな
く、加工性や電流効率の著しい低下を伴い工業的に有利
な方法はなかった。本発明は、上記問題点を解決し、C
rを含有する耐食性に優れた亜鉛系電気めっき鋼板の製
造方法を提供するものである。
Attempts to precipitate Cr together with zinc have conventionally been made using Cr 3+ or Cr 6+ ions, but only a small amount of Cr precipitates from a simple bath. Several% of C due to increase of Cr concentration and current density
Even when r is precipitated, not only good appearance is not obtained, but also there is no industrially advantageous method accompanied by remarkable reduction in workability and current efficiency. The present invention solves the above problems, and
An object of the present invention is to provide a method for producing a zinc-based electroplated steel sheet having excellent corrosion resistance containing r.

【0004】[0004]

【課題を解決するための手段】本発明の要旨は、 (1)Crを含有する電気亜鉛めっき鋼板を製造するに
際し、Zn2+イオン,Cr3+イオン及びバニリンも
しくはその誘導体を0.1〜10g/l含有し、pH
0.5〜3.0であるめっき浴を用いて、電流密度20
〜150A/dm 電気めっきを行なうことを特徴と
する耐食性に優れた亜鉛系電気めっき鋼板の製造方法。 (2)Crを含有する電気亜鉛めっき鋼板を製造するに
際し、Zn2+イオン,Cr3+イオン,バニリンもし
くはその誘導体を0.1〜10g/l、カチオンポリマ
ーおよび/またはポリオキシアルキレン誘導体を0.0
1〜20g/l含有し、pH0.5〜3.0であるする
めっき浴を用いて、電流密度20〜150A/dm
電気めっきを行なうことを特徴とする耐食性に優れた亜
鉛系電気めっき鋼板の製造方法である。
The gist of the present invention is as follows. (1) In producing a galvanized steel sheet containing Cr, 0.1 to 10 g / volume of Zn 2+ ion, Cr 3+ ion and vanillin or a derivative thereof. l , pH
With a plating bath of 0.5 to 3.0, a current density of 20
Method for producing a superior zinc electroplated steel sheet in corrosion resistance, characterized in that at ~150A / dm 2 perform electroplating. (2) In producing a galvanized steel sheet containing Cr, 0.1 to 10 g / l of Zn 2+ ion, Cr 3+ ion, vanillin or a derivative thereof, and 0.00 to 0.1 g of a cationic polymer and / or a polyoxyalkylene derivative.
Excellent corrosion resistance characterized in that electroplating is performed at a current density of 20 to 150 A / dm 2 using a plating bath containing 1 to 20 g / l and having a pH of 0.5 to 3.0 . This is a method for producing a zinc-based electroplated steel sheet.

【0005】[0005]

【作用】従来Zn2+イオンとCr3+ないしはCr6+イオ
ンからなる単純浴を使用しても微量のCrが析出するの
みであり、Cr濃度や電流密度の増加によって数%のC
rを析出させても、耐食性の向上代は小さく、また外観
や加工性の点で実用に耐えるめっきが得られなかった。
しかるに、Cr3+イオンを含む亜鉛系めっき浴中にバニ
リンもしくはバニリンの誘導体をCr析出促進剤として
添加することにより、この問題は解決され、多量のCr
を含む高度の耐食性を有するめっきが得られるようにな
る。この理由は、バニリンがCr3+イオンと錯体を形成
し、Zn2+イオンの析出を抑制しつつCr3+イオンの析
出を容易ならしめるためと推定される。バニリンもしく
はバニリンの誘導体の添加量は0.1〜10g/lが好
ましく、0.1g/l未満ではCr析出効果が十分では
なく、10g/lを超えるとめっき浴に溶解し難くなる
ので実用的ではない。ここで、バニリンとはC8 8
3 で示される有機化合物であり、
The use of a simple bath of conventional Zn 2+ ions and Cr 3+ or Cr 6+ ions only precipitates a small amount of Cr.
Even when r was precipitated, the margin of improvement in corrosion resistance was small, and plating that could withstand practical use in terms of appearance and workability could not be obtained.
However, by adding vanillin or a derivative of vanillin as a Cr deposition accelerator to a zinc-based plating bath containing Cr 3+ ions, this problem was solved, and a large amount of Cr was added.
Thus, plating having a high corrosion resistance including the above can be obtained. The reason is presumed to be that vanillin forms a complex with Cr 3+ ions and facilitates the precipitation of Cr 3+ ions while suppressing the precipitation of Zn 2+ ions. The addition amount of vanillin or a derivative of vanillin is preferably 0.1 to 10 g / l, and if it is less than 0.1 g / l, the effect of Cr precipitation is not sufficient. is not. Here, vanillin is C 8 H 8 O
An organic compound represented by 3 ,

【0006】[0006]

【化1】 Embedded image

【0007】バニリンの誘導体とはバニリン酸,バニリ
ンオキシム,あるいはこれらのエステル類などを含む。
バニリンとその誘導体は単独,もしくは複合で用いられ
てよい。めっき浴中には、これらバニリン類の他にさら
にカチオンポリマーあるいはポリオキシアルキレン誘導
体を添加してもよく、これにより外観品位を向上させる
ことができ、また、Cr析出に対してもより有利であ
る。これらの添加量は0.01〜20g/lが好まし
く、0.01g/l未満では上記効果が不足し、20g
/lを超えるとCr析出効果が飽和する。カチオンポリ
マーとポリオキシアルキレン誘導体は、何れか一方を用
いてもよいし、両方を用いてもよい。
The derivatives of vanillin include vanillic acid, vanillin oxime, and esters thereof.
Vanillin and its derivatives may be used alone or in combination. In the plating bath, a cationic polymer or a polyoxyalkylene derivative may be further added in addition to these vanillins, whereby the appearance quality can be improved, and it is more advantageous for Cr precipitation. . The addition amount of these is preferably 0.01 to 20 g / l, and if the addition amount is less than 0.01 g / l, the above effect is insufficient and 20 g / l
If it exceeds / l, the Cr precipitation effect is saturated. Either the cationic polymer or the polyoxyalkylene derivative may be used, or both may be used.

【0008】カチオンポリマーとしては、次に示す4級
アミン塩の重合物が好ましく、特にポリアミンスルホン
(PASと略)及びポリアミン(PAと略)が効果的で
ある。この理由としては、アミン基による陰極面への吸
着作用とスルホン基へのCr 3+イオンの配位結合が寄与
していると推定される。平均分子量としては102 〜1
6 が好ましい。
[0008] As the cationic polymer, the following quaternary
Polymers of amine salts are preferred, especially polyamine sulfones
(Abbreviated as PAS) and polyamine (abbreviated as PA) are effective
is there. The reason for this is that amine groups absorb
Adhesion and Cr on sulfone groups 3+Coordination bond of ion contributes
It is estimated that The average molecular weight is 10Two ~ 1
06 Is preferred.

【0009】[0009]

【化2】 Embedded image

【0010】[0010]

【化3】 Embedded image

【0011】[0011]

【化4】 Embedded image

【0012】ポリオキシアルキレン誘導体は、R2 −O
−(R1 −O)n −Hで示される有機化合物である。平
均分子量としては、102 〜106 が好ましい。このう
ち、特にポリエチレングリコール(PEGと略)HO−
(CH2 −CH2 −O)n −Hが有効である。
The polyoxyalkylene derivative is represented by R 2 —O
It is an organic compound represented by-(R 1 -O) n -H. The average molecular weight, 10 2 to 10 6 are preferred. Among them, polyethylene glycol (abbreviated as PEG) HO-
(CH 2 —CH 2 —O) n -H is effective.

【0013】図1には上記Cr析出促進剤の添加量とめ
っき層中のCr含有率の関係,図2には上記Cr析出促
進剤の添加量と得られためっき皮膜の外観の関係を示
す。Cr析出促進剤添加量以外の条件,すなわち、めっ
き浴組成,めっき条件は一定である。バニリン0.1g
/l未満ではCr含有率は1%程度であるが、0.1g
/l以上になるとCr含有率は5%以上になる。また、
カチオンポリマーの1例としてPAを1g/l添加する
と、Cr含有率はバニリン単独の場合に比較して増加す
る傾向にあり、かつ光沢のある均一な外観が得られるよ
うになる。
FIG. 1 shows the relationship between the amount of the Cr deposition accelerator added and the Cr content in the plating layer, and FIG. 2 shows the relationship between the amount of the Cr deposition accelerator added and the appearance of the plating film obtained. . The conditions other than the amount of the Cr precipitation accelerator added, that is, the plating bath composition and the plating conditions are constant. Vanillin 0.1g
/ L, the Cr content is about 1%, but 0.1 g
/ L or more, the Cr content becomes 5% or more. Also,
When 1 g / l of PA is added as an example of the cationic polymer, the Cr content tends to increase as compared with the case of vanillin alone, and a glossy uniform appearance is obtained.

【0014】めっき浴の種類は特に制約されないが、硫
酸塩浴,塩化物浴,これらの混合浴が望ましい。金属イ
オン濃度については、Zn2+イオン,Cr3+イオン,鉄
族金属2価イオンの合計で30〜200g/lが好まし
い。30g/l未満では高電流密度でイオンの供給不足
となりやすく、結果的にめっき焼けを生じやすい。20
0g/lを超えると、ドラッグアウトによるイオンの浪
費が無視できなくなると共に、液温が低くなった場合の
結晶化の懸念を生じる。その他のめっき条件について
は、特に制約されるものではないが、pH0.5〜3,
浴温40〜70℃、液流速1m/min以上,電流密度
20A/dm2 以上が好ましい範囲であり、目的とする
めっき組成,電流効率を考慮して最適な条件を採用する
ことができる。めっき浴中には、Na+ , NH4 + など
の電導度助剤,耐食性をさらに向上させるためのSiO
2 ,TiO2 ,Al2 3 などの酸化物粒子,BaCr
4などのクロム酸塩粒子を添加してもよく、本発明の
製造方法に本質的な支障はない。
The type of plating bath is not particularly limited, but a sulfate bath, a chloride bath, and a mixed bath thereof are preferred. The metal ion concentration is preferably 30 to 200 g / l in total of Zn 2+ ions, Cr 3+ ions, and iron group metal divalent ions. If it is less than 30 g / l, the supply of ions tends to be insufficient at a high current density, and as a result, burning of the plating tends to occur. 20
If it exceeds 0 g / l, waste of ions due to drag-out cannot be ignored, and crystallization may occur when the liquid temperature is lowered. Other plating conditions are not particularly limited, but have a pH of 0.5 to 3,
The preferred ranges are a bath temperature of 40 to 70 ° C., a liquid flow rate of 1 m / min or more, and a current density of 20 A / dm 2 or more. Optimal conditions can be adopted in consideration of the desired plating composition and current efficiency. In the plating bath, conductivity aids such as Na + , NH 4 + and SiO for further improving corrosion resistance are used.
2, the oxide particles, such as TiO 2, Al 2 O 3, BaCr
Chromate particles such as O 4 may be added, and there is no essential problem in the production method of the present invention.

【0015】かくしてCrと鉄族金属を含有する電気亜
鉛めっき鋼板を製造することができるが、めっき層中の
Cr含有率については、5〜30%が好ましい。5%未
満でも亜鉛めっきに比較すれば耐食性の向上は認められ
るが、5%以上になると亜鉛めっきはもとよりZn−N
i,Zn−Feなどの合金めっきを上回る高耐食性を発
揮し、例えば塩水噴霧試験を500時間以上行なっても
容易に赤錆は発生しない。この理由は、CrはZnとの
共存下では不働態化せずZnとともに犠牲防食作用を発
揮するが、めっき表面に形成される腐食生成物は難溶性
の保護皮膜として機能し、めっき層内部への腐食因子の
侵入を抑制するためと推定される。Cr含有率が30%
を超えると、加工性が低下するため、好ましくない。ま
た、Cr析出促進剤であるバニリンもしくはバニリンの
誘導体,ないしはカチオンポリマーやポリオキシアルキ
レン誘導体をめっき層中に微量共析させても差し支えな
く、5%以下の共析率ならば緻密で均一なめっき層が形
成され成形性に有利である。
Thus, an electrogalvanized steel sheet containing Cr and an iron group metal can be manufactured, but the Cr content in the plating layer is preferably 5 to 30%. Even if less than 5%, an improvement in corrosion resistance is recognized in comparison with zinc plating, but if it is 5% or more, not only zinc plating but also Zn-N
It exhibits higher corrosion resistance than alloy plating of i, Zn-Fe, etc., and does not easily generate red rust even if, for example, a salt spray test is performed for 500 hours or more. The reason is that Cr does not passivate in the presence of Zn and exhibits sacrificial corrosion protection together with Zn, but the corrosion products formed on the plating surface function as a hardly soluble protective film, and It is presumed to suppress the invasion of corrosion factors. 30% Cr content
If it exceeds, the workability is lowered, which is not preferred. In addition, vanillin or a derivative of vanillin, or a cationic polymer or a polyoxyalkylene derivative, which is a Cr deposition accelerator, may be co-deposited in a small amount in the plating layer. A layer is formed, which is advantageous for moldability.

【0016】[0016]

【実施例】冷延鋼板を、アルカリ脱脂し、5%硫酸水溶
液で酸洗した後、表1及び表2に示す条件で電気めっき
を行なった。Cr析出促進剤のうち、カチオンポリマー
としては平均分子量1万のPA、平均分子量3500の
PAS,ポリオキシアルキレン誘導体としては平均分子
量1500のポリエチレングリコールを用いた。めっき
浴としては硫酸塩浴を用い、めっき付着量は20g/m
2 とした。こうして得られためっき組成と耐食性,外観
の評価を表2に示す。耐食性は塩水噴霧試験(JIS
Z2371に準拠)を500時間行ない、以下の要領で
判定した。
EXAMPLE A cold-rolled steel sheet was degreased with alkali and pickled with a 5% aqueous sulfuric acid solution, and then electroplated under the conditions shown in Tables 1 and 2. Among the Cr precipitation accelerators, PA having an average molecular weight of 10,000, PAS having an average molecular weight of 3500 as a cationic polymer, and polyethylene glycol having an average molecular weight of 1500 as a polyoxyalkylene derivative were used. A sulfate bath was used as the plating bath, and the coating weight was 20 g / m2.
And 2 . Table 2 shows the evaluations of the plating composition, corrosion resistance, and appearance thus obtained. Corrosion resistance is measured by salt spray test (JIS
(According to Z2371) for 500 hours, and was determined in the following manner.

【0017】◎:赤錆発生1%以下 ○:赤錆発生10
%以下 △:赤錆発生50%以下 ×:赤錆発生50%超 めっき外観については、めっき表面の光沢度(JIS
Z8741 Gs(60°),黒色ガラス板基準値9
3)を測定し、以下の要領で判定した。 ◎:光沢度30以上 ○:光沢度20以上 △:光沢度
10以上 ×:光沢度10未満
◎: Red rust generation 1% or less :: Red rust generation 10
% Or less △: Red rust generation 50% or less ×: Red rust generation 50% or more For the plating appearance, the glossiness of the plating surface (JIS)
Z8741 Gs (60 °), black glass plate standard value 9
3) was measured and determined in the following manner. :: Gloss 30 or more :: Gloss 20 or more Δ: Gloss 10 or more ×: Gloss less than 10

【0018】表1,表2において、比較例1はめっき浴
のバニリンが少ないために、Crの析出量が少なく耐食
性が不良である。比較例2は比較例1と同一のめっき浴
組成で電流密度を高くしてCrを析出させたが、十分な
Cr含有率が得られていないため、耐食性が不足すると
共に、外観も不良である。比較例3はZn−Ni合金め
っきであり、外観は良好なものの耐食性は本発明例を下
回る。これらに対して、本発明例は何れもCr含有率5
%以上のめっきが得られ、耐食性,外観共に良好であ
る。また本発明例5〜11はバニリン類とカチオンポリ
マーもしくはポリオキシアルキレン誘導体を併用した例
であるが、本発明例1〜4のバニリン類単独使用の例に
比し、外観が一段と向上し、Cr含有率も高くなる結果
が得られた。
In Tables 1 and 2, Comparative Example 1 has a small amount of Cr precipitation and poor corrosion resistance due to a small amount of vanillin in the plating bath. In Comparative Example 2, Cr was deposited by increasing the current density with the same plating bath composition as Comparative Example 1, but a sufficient Cr content was not obtained, so that the corrosion resistance was insufficient and the appearance was poor. . Comparative Example 3 is a Zn-Ni alloy plating, and although the appearance is good, the corrosion resistance is lower than that of the present invention. On the other hand, all of the examples of the present invention have a Cr content of 5%.
% Of plating is obtained, and both corrosion resistance and appearance are good. Examples 5 to 11 of the present invention are examples in which vanillins are used in combination with a cationic polymer or a polyoxyalkylene derivative, and the appearance is further improved as compared with the examples of vanillins used alone in Examples 1 to 4 of the present invention, The result that the content rate also became high was obtained.

【0019】[0019]

【表1】 [Table 1]

【0020】[0020]

【表2】 [Table 2]

【0021】[0021]

【発明の効果】以上述べた如く、本発明は、特定の添加
剤をめっき浴に仕込むことにより、従来困難であった電
気亜鉛めっき中へのCrの共析を可能とし、耐食性に極
めて優れた電気亜鉛めっき鋼板を製造するものである。
したがって、自動車車体用途を中心に高耐食性が要求さ
れる防錆鋼板を製造する上で極めて効果的である。
As described above, according to the present invention, by adding a specific additive to a plating bath, it is possible to co-deposit Cr into electrogalvanized plating, which has been difficult in the past, and to achieve extremely excellent corrosion resistance. It is for producing electrogalvanized steel sheets.
Therefore, it is extremely effective in producing a rust-preventive steel sheet requiring high corrosion resistance mainly for an automobile body.

【図面の簡単な説明】[Brief description of the drawings]

【図1】めっき浴中へのバニリン及びPAの添加量とめ
っき層中のCr含有率の関係を示す図、
FIG. 1 is a diagram showing the relationship between the amounts of vanillin and PA added to a plating bath and the Cr content in a plating layer;

【図2】めっき浴中へのバニリン及びPAの添加量と得
られためっき皮膜の外観との関係を示す図である。
FIG. 2 is a diagram showing the relationship between the amount of vanillin and PA added to a plating bath and the appearance of a plating film obtained.

Claims (2)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 Crを含有する電気亜鉛めっき鋼板を製
造するに際し、Zn2+イオン,Cr3+イオン及びバ
ニリンもしくはその誘導体を0.1〜10g/l含有
し、pH0.5〜3.0であるめっき浴を用いて、電流
密度20〜150A/dm 電気めっきを行なうこと
を特徴とする耐食性に優れた亜鉛系電気めっき鋼板の製
造方法。
When producing an electrogalvanized steel sheet containing Cr, 0.1 to 10 g / l of Zn 2+ ion, Cr 3+ ion and vanillin or a derivative thereof are contained.
And, using a plating bath which is PH0.5~3.0, current
A method for producing a zinc-based electroplated steel sheet having excellent corrosion resistance, wherein electroplating is performed at a density of 20 to 150 A / dm 2 .
【請求項2】 Crを含有する電気亜鉛めっき鋼板を製
造するに際し、Zn2+イオン,Cr3+イオン,バニ
リンもしくはその誘導体を0.1〜10g/l、カチオ
ンポリマーおよび/またはポリオキシアルキレン誘導体
を0.01〜20g/l含有し、pH0.5〜3.0で
あるするめっき浴を用いて、電流密度20〜150A/
dm 電気めっきを行なうことを特徴とする耐食性に
優れた亜鉛系電気めっき鋼板の製造方法。
2. When producing an electrogalvanized steel sheet containing Cr, 0.1 to 10 g / l of Zn 2+ ion, Cr 3+ ion, vanillin or a derivative thereof, and 0 to 10 g of a cationic polymer and / or a polyoxyalkylene derivative. 0.1 to 20 g / l at pH 0.5 to 3.0
Using a certain plating bath, a current density of 20 to 150 A /
A method for producing a zinc-based electroplated steel sheet having excellent corrosion resistance, wherein electroplating is performed at dm 2 .
JP5004095A 1993-01-13 1993-01-13 Manufacturing method of zinc-based electroplated steel sheet with excellent corrosion resistance Expired - Fee Related JP2711973B2 (en)

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Application Number Priority Date Filing Date Title
JP5004095A JP2711973B2 (en) 1993-01-13 1993-01-13 Manufacturing method of zinc-based electroplated steel sheet with excellent corrosion resistance

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JPH06212481A JPH06212481A (en) 1994-08-02
JP2711973B2 true JP2711973B2 (en) 1998-02-10

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2769614B2 (en) * 1986-06-04 1998-06-25 ディップソール 株式会社 Zinc-nickel alloy plating bath
JPH0635673B2 (en) * 1987-08-26 1994-05-11 新日本製鐵株式会社 Method for producing zinc-chromium electroplated steel sheet excellent in surface quality and corrosion resistance
JPS6479393A (en) * 1987-09-22 1989-03-24 Nippon Steel Corp Production of zinc-chromium electroplated steel sheet
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